N-phenyl sulfenamides



United States Patent U.S. Cl. 260551 4 Claims ABSTRACT OF THE DISCLOSURE Compounds of the formula wherein R is a cyano or nitro group in the para or meta position or a trifluoromethyl group, R is hydrogen or alkyl of 1 to 3 carbon atoms when R is cyano or nitro and R is hydrogen when R is trifluoromethyl, R is a polyhaloalkyl group having 1 to 2 carbon atoms and 3 to halogens of atomic number 17 to 35, at least one of the halogens being bonded to the or. carbon atom, a polyhalovinyl group wherein the halogens are of atomic number 17 to 35 or a l-halo-l-nitroalkyl group having 2 to 4 carbon atoms wherein the halogen has an atomic number of 17 to 35 and n is 1 or 2 when R is said polyhaloalkyl group and n is 1 when R is said l-halo-l-nitroalkyl group or said polyhalovinyl group. Compounds having the above formula are fungicidal.

CROSS REFERENCE TO RELATED APPLICATIONS This invention pertains to unique sulfenamides. More particularly, it relates to new N-phenyl sulfenamides and their use as pesticides.

INVENTION DESCRIPTION The sulfenamides of this invention have the general formula:

in which R is a cyano or nitro group in the para or meta (3 or 5) position or a trifiuoromethyl group in position 3-6 (ortho, para or meta) and R is hydrogen or alkyl of 1 to 3 carbon atoms when R is cyano or nitro and R is hydrogen when R is trifluoromethyl, R is a polyhaloalkyl group having 1 to 2 carbon atoms and 3 to 5 halogens of atomic number 17 to 35, preferably 17, at least one of said halogens being bonded to the 1 (alpha) carbon atom, a polyhalovinyl group wherein the halogens are of atomic number 17 to 35, preferably 17, or a 1 halo-1- nitroalkyl group having 2 to 4 carbon atoms, wherein the halogen is of atomic number 17 to 35, preferably 17, and n is 1 or 2 when R is said polyhaloalkyl group, and n is 1 when R is said 1-halo-1-nitroalkyl group or said polyhalovinyl group. Preferably R is hydrogen, R is a cyano or nitro group in the para or meta position, 11 is 1 and R is a polyhaloethyl group having 3-5 halogens of atomic number 17 to 35, at least one of which is bonded to the alpha carbon atom. Even more preferably R is hydrogen, R is a p-nitro group, R is 1,2,2.,2-tetrachloroethyl and n is l.

Examples of compounds having the above general formula are:

N-p-nitrophenyl-trichloromethane sulfenamide,

N-m-cyanophenyl-trichloromethane sulfenamdie,

N- 2-methyl-5-nitrophenyl) -tribromomethane sulfenamide,

N-pcyanophenyl-pentachloroethane thiosulfenamide,

N -m-nitrophenyl-1-chloro-2,2-dibromoethane sulfenamide,

N-(2-methyl-4-nitrophenyl)-1-bromo-1,2,2-trichloroethane sulfenamide,

N- 3-cyano-2-methylphenyl) -trichloromethane thiosulfenamide,

N-p-trifluoromethylphenyl-1,1,2,2-tetrachloroethane sulfenamide,

N-5-trifluoromethylphenyl-pentachloroethane sulfenamide,

N- (5-cyano-2ethylphenyl) -1,2,2,2--tetrachloroethane sulfenamide,

N-p-nitrophenyl-l,1,2,2-tetrabromoethane sulfenamide,

N-(3-nitro-2-propylphenyl)-1,1,2-trichloroethane sulfenamide,

N-p-cyanophenyl-trichlorovinyl sulfenamide,

N-m-nitrophenyl-Z,2-dichloroviny1 sulfenamide,

N-(4-cyano-2-methylphenyl)-2,2-di1bromovinyl sulfenamide,

N-3-trifluoromethylphenyl-trichlorovinyl sulfenamide,

N-p-nitrophenyl-1,2-dich1orovinyl sulfenamide,

N-m-cyanophenyl-l-chloro-1-nitroethane sulfenamide,

N-p-nitrophenyl-l-chloro-l-nitropropane sulfenamide,

N-(2-methyl-5-nitrophenyl) -1-bromo-1-nitropropane sulfenamide,

N-p-cyanophenyl-l-chloro-l-nitrobutane sulfenamide,

N-p-trifluoromethylphenyl-1,1,2,2-tetrachloroethane sulfenamide,

N-o-trifluoromethylphenyltrichlorovinyl sulfenamide and Nm-trifluoromethylphenyl-1-chloro-l-nitroethane sulfenamide.

These sulfenamides may be made by reacting mor pnitroaniline, mor p-cyanoaniline or a trifluoromethylaniline with a polyhaloalkylsulfenyl or thiosulfenyl halide, polyhalovinylsulfenyl halide or l-halo-l-nitroakylsulfenyl halide.

Polyhaloalkylthiosulfenyl halides are disclosed in US. Pat. No. 3,234,272. Polyhaloethylsulfenyl halides are disclosed in US. Pats. Nos. 3,178,447 and 3,200,146. Polyhalovinylsulfenyl halides are discolsed in US. Pats. Nos. 3,296,302 and 3,155,720. l-halo-l-nitroalkylsulfenyl halides and their method of preparation are disclosed in applicants applications Ser. Nos. 442,812, filed Mar. 25, 1965, now abandoned, and 711,510, filed Mar. =8, 1968, the texts of which are hereby incorporated by reference. Sulfenyl chlorides are preferred. Alternatively, the polyhalovinyl sulfenamides may be made by dehydrohalogenating agent such as tertiary amines, stro'ng alkalis or alkali carbonates may be used.

The sulfenyl halide-aniline reaction may be carried out neat or in the presence of aqueous solvents such as chloroform-water, benzene-water, toluene-water, etherwater and hexane-water. Temperatures ranging from 0 to 50 C. and subor superatmospheric pressures may be used if desired. However, the reaction may be con viently done at ambient temperature and atmospheric or autogenous pressures. Stoichiometric or excess proportions of sulfenyl halide, preferably excess, will be used.

3 EXAMPLES The following examples illustrate the novel sulfenamides of this invention and methods by which they may be made. These examples are offered only to illustrate these compounds and methods; they are not intended to limit the invention described and claimed herein.

Example 1 27.6 g. p-nitroaniline was suspended in 150 ml. chloroform in a flask. 125 ml. water and 40 ml. 1,2,2,2-tetrachloroethylsulfenyl chloride were added to this mixture. The combined mixture was stirred at room temperature for /2 hrs. and then allowed to stand overnight. The mixture was filtered and the solids were washed consecutively with dilute aqueous HCl, water and mixed hexanes. 51.5 g. N p nitrophenyl-1,2,2,2,Z-tetrachloroethane sulfenamide was recovered. This compound was observed as a yellow-brown solid which melted at 129132 C. Its analysis was: (wt. percent) Clcalcd 42.20, found 42.08; Scalcd 9.54, found 9.57.

Example 2 11.8 g. p-cyanoaniline and 100 ml. CHCl were put in a vessel. To this solution 100 ml. water and 20 ml. 1,1,2,2- tetrachloroethylsulfenyl chlorides were added. The mixture was stirred at room temperature for 5-6 hrs. and then filtered. The solids were Worked up by dissolving 4 was: Clcalcd 13.44, found 13.58; Scalcd 12.15, found 11.5.

Example 4 11.4 g. of N-m-nitrophenyl-l,1,2,2-tetrachloroethane sulfenamide and 150 ml. ether were put in a vessel. A solution of 1.9 g. potassium hydroxide in 100 ml. methanol was added dropwise to the sulfenamide-ether mixture. A precipitate formed. The combined mixture was filtered and the solvent was stripped off the filtrate. The stripped filtrate was distilled to 60 C., 0.5 mm. Hg. 6.0 g. of N- m-nitrophenyl-trichlorovinyl sulfenamide were recovered. Its structure was verified by infrared analysis.

Example 5 TABLE I Analysis (wt. percent) Chlorine Sulfur Melting point,

Compound Calculated Found Calculated Found C.

N-p-nitrophenyl-l,1,2,2-tetrachlor0ethane sulfenamide 42. 21 40. 80 9. 54 9. 94 127-129 N-pmitrOphenyl-tfiehlorornethane sulfenamide 36, 99 37. 9 11. 15 10. 9 150-152 N-m-nitrophenyl-l,1,2,2-tetraehl0roethane sulfenamide. 42. 21 41. 25 9. 54 9. 57 104-106 N-p-cyanophenyl-1,1,2 2-tetrachloroethane sulienamide- 44. 87 44. 10. 14 10. 18 135-136 N-m-nitrophenyl-triehloromethane sulfenamide 36. 98 35. 11. 15 12. 30 99-102 N-p-eyanophenyl-pentachloroethane sulfenamide 50, 58 49. 00 9. 14 9. 40 140-142 N-m-nitrophenyl-l,2,2,2-tetrachloroethane sulfenamide 42. 21 44. 00 9. 54 9. 16 106-107 N-m-nitrophenyl-pentachloroethane sullenamide 47. 85 45. 41 8. 65 8. 38 103-105 N-p-cyanophenyl-1,2,2,2-tetrachloroethane sulfenamide 44. 87 44. 10. 14 9. 69 160-151 N-(2-methyl-5-nitrophenyl)-1,1,2,2-tetrachloroethane sulfenamide 40. 40. 75 9. 16 9. 07 113-116 N-(2-methyl-4-nitrophenyl)-1,1,2,2-tetraehloroethane sulfenamide.. 40. 55 38. 30 9. 16 8. 33 104-109 N-(2-methyl-4-nitrophenyl)-1,2,2,2-tetrachloroethane sulfenamide. 40. 55 40. 35 9. 16 9. 38 107-111 N-(2-methyl-5-nitrophenyl)-1,2,2,2-tetraehloroethane sulfenamida. 40. 55 40. 05 9. 16 9. 39 102-104 N-(2-rnethyl-5-nitrophenyl)-trichloromethane sulfenamide 35. 27 33. 10. 63 11. 77 145-148 N-p-nitrophenyl-trichloromethane thiosulfenamide- 33. 28 34. 2 20. 06 19. 87 112-115 N-m-nitrophenyl-trichloromethane thiosulfenamide 33. 28 33. 95 20. 06 21. 18 110-111 N-p-cyano henyl-trichloromethane thiosulfcnamide 35. 54 36. 35 21. 43 21. 45 144-145 N-p-nitrop enyl-trichlorovinyl sulfenamitle 35. 51 33. 13 10. 70 9. 95 1051-108);

N-(Z-methyl-S-nitrophenyl)-trichlorovinyl sullonamide- 33. 91 33. 5 10. 22 9. 84 90-91 N-p-cyanophenyl-trichlorovinyl sulfenamide 38. 05 37. 47 11. 47 11. 00 112-115 N-o-trifiuoromethylphenyl-l,2,2,2-tetrachloroethane sulfenamide- *11. 2 *12. 42 8. 93 9. 63 57-63 N-o-trifluoromethylphenyl-l,2,Z-trichloroethane sulfenamide 32. 76 34. 75 9. 87 10. 44 N-p-trifluoromethylpl1enyl-1,2,2-trichloroethane sulfenamide 32. 76 34. 02 9. 87 10. 27 N-m-trifluoromethylphenyl-l,2,2-trichloroethane sullemrmide- 32. 76 34. 40 9. 87 10. 46 N-m-trifiuoromcthylphenyl-trichloromethylthio sulfenamide 31. 04 31. 42 18. 71 18. 45

them in CHCl and stripping off the solvent. The filtrate was put in a separatory funnel and the aqueous layer was removed. The organic layer was dried over MgSO and filtered. The solvent was stripped from it. The residue was added to the other solids giving 21.9 g. N-p-cyanophenyll,1,2,2-tetrachloroethane sulfenamide. It melted at 135- 136 C. and had the following weight percent analysis: Clcalcd 44.87, found 44.55; S-calcd 9.74, found 10.18.

Example 3 These unique sulfenamides may be used in toxic amounts to control or kill various pests, particularly fungi. The N-cyanoand nitrophenyl-1,2,2,2-tetrachloroethyl sulfenamides of this invention show excellent activity as ovicides, particularly as applied to acarid eggs such as two-spotted mite eggs.

sulfenamides of this invention were tested for fungitoxicity by The Standard Spore-Slide Germination Method for Determining Fungicidal Activity, described in the American Phytopathological Society Journal, vol. 33, pages 627-632 (1943). This method measures the fungitoxicity of compounds in terms of their percent inhibition of fungus spores. The general procedure was as follows: Each compound to be tested was dissolved in acetone to a concentration of 10 p.p.m. These solutions were then pipetted into the Wells of depression slides and allowed to dry. The wells were filled with a spore suspension of the specified test organism and incubated in a moist chamber overnight. A group of spores was examined and the number of spores germinated and not germinated was counted and recorded to show the biological activity in terms of the percentage germination inhibition. Table 11 reports the results of this testing.

be sprayed or otherwise applied to a plant, plant seed, other host or soil.

TABLE II Percent inhibition Monz'lt'm'a Alternarz'a Fusarimn Compound fructicola solani solam' N-p-nitrophenyl-l,1,2,Z-tetraohloroethane sulfenamide 100 100 N-p-nitrophenyl-trichlol'omethane sulfenarnide 98 100 N-m-nitrophonyl-l,1,2,2-tetraehlo1oethane sulienarnida. 22 97 N-p-cyanophenyl-l,1,2,2-tetrachloroethane sulfenamide 61 22 90 N-p-cyanophenyl-trichlorornethane sultenamide 78 78 N-m-nitrophenyl-trichloromethane sulienamide. 100 90 100 N-m-nitrophenyl-trichlorovinyl sulfenamide 97 22 100 N-p-cyanophenyl-pentachloroethane sulienamide- 100 97 N-m-nitrophenyl-l,2,2,2-tetraehloroethane sulfenamide 100 97 100 N-p-nitrophenyl-l,2,2,2-tetraehloroethane sulfenarnide. 100 100 100 N-p-eyanopheny1-1,2,2,2-tetraehloroethane sulfenamide 98 90 98 N-(2methyl-4-nitrophenyl)-1,1,2,2tetrachloroethane sulf 100 100 N-(2methyl5-nitropheny1)-1,2,2,2 tetrachloroethane sulfenamide 97 100 N-(2-methyl-5-nitrophenyl)-trichloromethane sulfenamide. 100 N-p-nitropheny1-trichloromethane thiosulienarnide 100 N-m-nitrophenyl-trichloromethane thiosulfenamide. 100 N-p-eyanophenyl-triehloromethane thiosulienamide-.. 100 N-m-nitrophenyl-l-ehloro-l-nitroethane sultenarmde N-O-trifluoromethylphenyl-l,2,2,2-tetraeh1oroethane sulfenamide N-p-t1ifluoromethylpenyl-1,2,2-t1iehloroethane sulfenamide 100 N-O-trifiuoromethylphenyl-l,2,2 trichloroethane sulfenamide 97 Ovicidal activity was tested using two-spotted mite (Tetranychus telarius L.) eggs on Ford Hook lima bean plants. The procedure was as follows: The sulfenamide to be tested was dissolved in acetone and water to a 100 p.p.m. concentration. Replicate lima bean leaves on which mites had laid eggs were dipped in the sulfenamide solution and then placed in an incubator at about 75 F. After two weeks the eggs, including shells of hatched eggs and dead eggs, were counted. Ovicidal activity expressed as percent inhibition was determined from the number of dead eggs compared to the total number of eggs counted. Table III reports the results of these tests on certain sulfenamides of this invention.

Aside from formulating and applying the sulfenamides as described above, they may be dispersed in or on other liquid and solid carriers such as inert clay, petroleum solvents and the like. The solid carrier may be a dust, wettable powder or pellet. And, these compounds may be formulated alone or together with other compatible pesticides, dispersing agents or other adjuvants.

As fungicides, these sulfenamides may be applied in fungitoxic amounts to any environmental area which hosts or is subject to attack from fungi such as, for example, those previously mentioned and Helminthosporium salivum, Pythium ultimum, Rhizoctom'a solani, F. phaseoli and the like. The fungicidal compositions may I claim: 1. A compound having the formula wherein R is a cyano or nitro group in the para or meta position or a trifiuoromethyl group, R is hydrogen or alkyl of 1 to 3 carbon atoms when R is cyano or nitro and R is hydrogen when R is trifluoromethyl, R is a polyhaloethyl group having 3 to 5 halogens of atomic number 17 to 35, at least one of the halogens being bonded to the a carbon atom, a polyhalovinyl group wherein the halogens are of atomic number 17 to 35 or a l-halo-l-nitroalkyl group having 2 to 4 carbon atoms wherein the halogen has an atomic number of 17 to 35 and n is 1 or 2 when R is said polyhaloethyl group and n is 1 when R is said l-halo-l-nitroalkyl group or said polyhalovinyl group.

2. A compound of claim 1 wherein R is hydrogen.

3. A compound of claim 1 wherein n is 1 when R is said polyhaloethyl group.

4. The compound of claim 1 wherein R is hydrogen, R is a nitro group in the para position and R is 1,2,2,2- tetrachloroethyl and n is 1.

References Cited Goerdeler et al., Berichte, vol. 95, pp. 1640-41 (1962).

HENRY R. JILES, Primary Examiner H. I. MONTZ, Assistant Examiner US. Cl. X.R. 424-3 20 

